Season both sides of the pork with salt and pepper.
Heat a large, deep skillet over medium-high heat with a tablespoon or so of olive oil.
Sear the pork roast in the skillet for 5 minutes per side or until a nice crust forms.
Turn off your stove top and place roast in to slow-cooker. De-glaze the pan the roast was in with chicken broth and add scrape up the brown bits at the bottom. Pour broth/pan juices into slow-cooker.
Add chopped onion, green pepper, rosemary and thyme into the slow cooker as well. Secure lid, set temp to high and cook for 8 hours undisturbed.
With 30 minutes remaining on the pork make the barbecue sauce. In a medium sauce pan combine the balsamic vinegar, ketchup, brown sugar, honey, mustard, Worcestershire, garlic, salt, pepper and cayenne. Whisk and bring to a simmer over medium-high heat. Let simmer for 20 minutes or until reduced by a third.
Meanwhile; remove the pork from the slow-cooker to a cutting board and drain the cooking liquids through a strainer to catch the peppers, onions and herbs. Add the veggies and herbs back to the slow-cooker and reduce the heat to low or warm.
For the pork; trim and discard any excess fat and shred with two forks. Add the pork back to the slow-cooker and pour in reduced balsamic-honey sauce. Stir to coat.
Split a corn muffin in half horizontally and top with pulled pork.
Garnish with chopped parsley and sliced pickled jalapenos if desired.